Preparation via microemulsion method and proton conduction at intermediate-temperature of BaCe1−xYxO3−α

The ceramic powders of BaCe_1?xY_xO_3?α (x = 0.05, 0.10, 0.15, 0.20) have been prepared via a microemulsion method. Green compacts of the powders were sintered to densities higher than 95% of theoretical at the lower temperature (1500 °C). The obtained ceramics showed a single-phase of orthorhombic perovskite. The proton conduction was investigated by employing the techniques of AC impedance and electrochemical hydrogen permeation (hydrogen pumping) at 300–600 °C. It was found that the ceramics were almost pure proton conductors in wet hydrogen, and the highest proton conductivity was observed for x = 0.15 at 600 °C. Ammonia was synthesized successfully from nitrogen and hydrogen at atmospheric pressure in the electrolytic cell using BaCe_0.85Y_0.15O_3?α. The maximum rate of NH₃ formation was found to be 2.1 × 10^?9 mol s^?1 cm^?2 at 500 °C with an applied current of 0.75 mA.     

Effects of calcination and activation temperature on dry reforming catalysts

The effect of calcination temperatures on dry reforming catalysts supported on high surface area alumina Ni/γ-Al₂O₃ (SA-6175) was studied experimentally. In this study, the prepared catalyst was tested in a micro tubular reactor using temperature ranges of 500, 600, 700 and 800 °C at atmospheric pressure, using a total flow rate of 33 ml/min consisting of 3 ml/min of N₂, 15 ml/min of CO₂ and 15 ml/min of CH₄. The calcination was carried out in the range of 500–900 °C. The catalyst is activated inside the reactor at 500–800 °C using hydrogen gas. It was observed that calcination enhances catalyst activity which increases as calcination and reaction temperatures were increased. The highest conversion was obtained at 800 °C reaction temperature by using catalyst calcined at 900 °C and activation at 700 °C. The catalyst characterization conducted supported the observed experimental results.     

Quantitative and kinetic TG-FTIR study of biomass residue pyrolysis: Dry distiller's grains with solubles (DDGS) and chicken manure

New energy policies all over the world are trying to tackle high oil prices and climate change by promoting the use of biomass to produce heat, electricity and liquid transportation fuels. In this paper we studied two different secondary fuels: dry distiller's grains with solubles (DDGS) and chicken manure. These materials have high content of nitrogen and ashes which limit their usage in thermal applications due to potential excessive NO_x emissions and problems of slagging, fouling, corrosion and loss of fluidization.The fuels tested here were received from industrial partners. In order to reduce the ash content the fuels were pre-treated using water leaching pre-treatment.Pyrolysis of these fuels has been monitored through a TG-FTIR set-up. Quantification of the following volatile species was possible: CO, CO₂, CH₄, HCN, NH₃, HNCO, H₂O.The water leaching appeared to decrease the amount of ashes in both samples and remove some of the troublesome compounds like Cl, S and K.The DDGS thermogravimetric curve showed three main peaks at 280 °C, 330 °C and 402 °C with a total weight loss of around 79%wt_a.r. (on an “as received” basis). NH₃ is the main N-compound released at low temperatures with a peak at 319 °C. HNCO and HCN were detected at higher temperatures of around 400 °C. Chicken manure reacted in four stages with peaks at 280 °C, 324 °C, 430 °C and 472 °C with a total average weight loss of 66%wt_a.r. The main N-compound was HNCO, released at 430 °C. Ammonia was detected during the whole measurement, while HCN presented peaks of reactivity at 430 °C and 472 °C.Kinetic analysis was applied using a distributed activation energy method (DAEM) using discrete and Gaussian distributions and data for further modeling purposes were retrieved and presented.     

H2 enriched fuels from co-pyrolysis of crude glycerol with biomass

Pyrolysis of glycerol has been identified as a possible route for producing high added value fuels like renewable hydrogen (H₂). Crude glycerol (CG) is the main byproduct of biodiesel industry and without purification it is a low added value material due to the presence of impurities. Co-pyrolysis of CG with biomass may improve the efficiency of the process and as a primary step of gasification give important information concerning the maximization of H₂ concentration in the produced gas. Moreover, the thermochemical treatment of crude glycerol–biomass mixtures may offer several economic and environmental advantages in biodiesel industry and reduce the cost of biodiesel production. A mixture of CG with olive kernel (OK) was used as pyrolysis feed material. Pyrolysis of a 25 wt% mixture of CG with OK at high temperature (T = 720 °C) seemed to promote steam reforming reactions leading to an increase of H₂ concentration of 11.6 vv% in the pyrolysis gas in comparison to H₂ in gas obtained by low temperature pyrolysis (T = 520 °C).     

Ni–Al hydrotalcite-like material as the catalyst precursors for the dry reforming of methane at low temperature

Nickel–aluminium and magnesium–aluminium hydrotalcites were prepared by co-precipitation and subsequently submitted to calcination. The mixed oxides obtained from the thermal decomposition of the synthesized materials were characterized by XRD, H₂-TPR, N₂ sorption and elemental analysis and subsequently tested in the reaction of methane dry reforming (DRM) in the presence of excess of methane (CH₄/CO₂/Ar = 2/1/7). DMR in the presence of the nickel-containing hydrotalcite-derived material showed CH₄ and CO₂ conversions of ca. 50% at 550 °C. The high values of the H₂/CO molar ratio indicate that at 550 °C methane decomposition was strongly influencing the DRM process. The sample reduced at 900 °C showed better catalytic performance than the sample activated at 550 °C. The catalytic performance in isothermal conditions from 550 °C to 750 °C was also determined.     

Thermal decomposition of lutetium propionate

The thermal decomposition of lutetium(III) propionate monohydrate (Lu(C₂H₅CO₂)₃·H₂O) in argon was studied by means of thermogravimetry, differential thermal analysis, IR-spectroscopy and X-ray diffraction. Dehydration takes place around 90 °C. It is followed by the decomposition of the anhydrous propionate to Lu₂O₂CO₃ with evolution of CO₂ and 3-pentanone (C₂H₅COC₂H₅) between 300 °C and 400 °C. The further decomposition of Lu₂O₂CO₃ to Lu₂O₃ is characterized by an intermediate constant mass plateau corresponding to a Lu₂O_2.5(CO₃)_0.5 overall composition and extending from approximately 550 °C to 720 °C. Full conversion to Lu₂O₃ is achieved at about 1000 °C. Whereas the temperatures and solid reaction products of the first two decomposition steps are similar to those previously reported for the thermal decomposition of lanthanum(III) propionate monohydrate, the final decomposition of the oxycarbonate to the rare-earth oxide proceeds in a different way, which is here reminiscent of the thermal decomposition path of Lu(C₃H₅O₂)·2CO(NH₂)₂·2H₂O.     

Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

Comparative study of the catalytic hydroconversion of cyclopentane over iridium and platinum single-crystal surfaces

In the context of fuel upgrading by selective ring opening of naphthenes, we have investigated the catalytic conversion of cyclopentane in large hydrogen excess over iridium and platinum single-crystal surfaces. Both (111) and (112) orientations have been considered. The catalytic tests have been performed at 1 kPa and 25–600 °C using a recently developed surface reactor equipped with laser heating and online gas chromatography. Only cyclopentene and C₁–C₄ cracking products are formed on iridium, while platinum additionally catalyzes the formation of pentane around 200 °C, which dehydrogenates to pentene at 250 °C. Noticeably, on both metals, the surface steps prevent hydrocarbon cracking (up to 400 °C) at the benefit of dehydrogenation. In all cases, a carbon overlayer is formed on the surfaces in the course of the reaction.     

Characterization of the different fractions obtained from the pyrolysis of rope industry waste

A study of the possibilities of pyrolysis for recovering wastes of the rope's industry has been carried out. The pyrolysis of this lignocellulosic residue started at 250 °C, with the main region of decomposition occurring at temperatures between 300 and 350 °C. As the reaction temperature increased, the yields of pyrolyzed gas and oil increased, yielding 22 wt.% of a carbonaceous residue, 50 wt.% tars and a gas fraction at 800 °C. The chemical composition and textural characterization of the chars obtained at various temperatures confirmed that even if most decomposition occurs at 400 °C, there are some pyrolytic reactions still going on above 550 °C. The different pyrolysis fractions were analyzed by GC–MS; the produced oil was rich in hydrocarbons and alcohols. On the other hand, the gas fraction is mainly composed of CO₂, CO and CH₄. Finally, the carbonaceous solid residue (char) displayed porous features, with a more developed porous structure as the pyrolysis temperature increased.     

Study on the cesium Tutton compounds,Cs2M(XO4)2∙6H2O (M = Mg,Co, Zn; X = S,Se): Preparation,X-ray powder diffraction and infrared spectra

The crystallization processes in the three-component systems Cs₂SO₄–MSO₄–H₂O (M = Mg, Co, Zn) have been studied at 25 °C. It has been established that cesium Tutton compounds, Cs₂M(SO₄)₂·6H₂O (M = Mg, Co, Zn; X = S, Se), crystallize from the ternary solutions within large concentration ranges. The double salts were identified by means of X-ray powder diffraction and infrared spectroscopy. Infrared spectra of the cesium compounds are presented and discussed with respect to both the normal modes of the tetrahedral ions and the water molecules. The water librations are also discussed. The strength of the hydrogen bonds formed in the cesium salts as deduced from the frequencies of ν_OH is commented. The analysis of the spectra reveals that stronger hydrogen bonds are formed in the cesium selenates as compared to those in the respective sulfates due to the stronger proton acceptor ability of the selenate ions.     

An investigation on the solid state pyrolytic decomposition of bimetallic oxalate precursors of Ca,Sr and Ba with cobalt: A mechanistic approach

The mixed metal oxalate precursors, calcium(II)bis(oxalato)cobaltate(II)hydrate (COC), strontium(II)bis(oxalato)cobaltate(II)pentahydrate (SOC) and barium(II)bis(oxalato)cobaltate(II)octahydrate (BOC) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound COC decomposed mainly to CaC₂O₄ and Co₃O₄ at 340 °C, and a mixture of CaCO₃ and Co₃O₄ identified at 510 °C. A mixture of CaCO₃ and Ca₃Co₂O₆ along with the oxides and carbides of both the cobalt and calcium were attributed at 1000 °C as end products. DSC study in nitrogen ascertained the formation of a mixture of CaO and CoO along with a trace of carbon at 550 °C. The mixture species, SrC₂O₄, CoC₂O₄ and Co₃O₄ were generated at 255 °C in case of SOC in air, which ultimately changed to CoSrO₃, SrCO₃ and oxides of strontium and cobalt at 1000 °C. The several mixture species also generated as intermediate at 332 and 532 °C. The DSC study in nitrogen indicated the formation of CoSrO_x (0.5 < x < 1) as end product. In case of BOC in air, a mixture of BaCoO₂, BaO, CoO and carbides are identified as end product at 1000 °C through the generation of several intermediate species at 350 and 530 °C. A mixture of BaO and CoO is identified as end product in DSC study in nitrogen. The kinetic parameters have been evaluated for all the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the kind of dominance of kinetic control mechanism of the dehydration and decomposition steps are also inferred. The kinetic parameters, ΔH and ΔS of all the steps are explored from the DSC studies. Some of the decomposition products are identified by IR and X-ray powder diffraction studies.     

Comparison of gasification and pyrolysis of thermal pre-treated wood board waste

The second step of a two-step process of thermo-chemical conversion of wood board waste is discussed in this paper. GC-TCD and FTIR analyses of the gas product enable to compare the two proposed way: pyrolysis and gasification of the pre-treated and virgin wood board sample between 800 and 1000 °C. The effect of the first step of the process (low-temperature pyrolysis which aims to remove nitrogen initially present in wood board waste) has shown to be really efficient as the production of ammonia observed during the second step decreases by a factor 6–8 jointly to a slight decrease of the energy recovery. The first step also prevents the production of hydrogen cyanide and is therefore essential. Concerning pre-treated samples, the best results have been obtained at 1000 °C with samples pre-treated at 250 °C. The way of gasification has been shown to be more efficient in term of energy recovery but leads to a production of ammonia larger than in the case of the pyrolysis way. The conversion of the pyrolysis residual char into an activated char must be considered since it presents a potential economic interest.     

Catalytic pyrolysis of Phragmites (reed): Investigation of its potential as a biomass feedstock

In this paper, thermogravimetry, TG, and pyrolysis are used for the thermochemical evaluation of the common reed (Pragmites australis) as a candidate biomass feedstock. The TG analysis indicated that the material loses 4% of its weight below 150 °C through dehydration. The main decomposition reaction occurs between 200 and 390 °C. The rate of weight loss, represented by the derivative thermogravimetric, DTG, signal indicated a multi-step reaction. Kinetic analysis helped in the resolution of the temperature ranges of the overlapping steps. The first step corresponds to the degradation of the hemi-cellulosic fraction and the second to the cellulosic fraction degradation. The TG and DTG signals of reed samples treated with increasing concentration of potassium carbonate (0.6–10 wt%) indicated a catalytic effect of the salt on reed decomposition. The temperature of maximum weight loss rate, DTGmax, exponentially decreased with increasing catalyst content, whilst the initial temperature of the decomposition decreased linearly. The pyrolysis studies were carried out in a Pyrex vertical reactor with sintered glass disc to hold the sample and to aid the fluidization with the nitrogen stream flowing upwards. The reactor was connected to a cyclone and condenser and a gas sampling device. Tar and char are collected and weighed. The gas chromatographic analysis of the evolved gases demonstrated the effect of pyrolysis temperature (400, 450, and 500 °C) on their composition. The temperature increase favors the yields of hydrocarbons, carbon monoxide and hydrogen at the expense of methanol and carbon dioxide. Similarly, reed samples treated with K2CO3 at 10 wt% were pyrolyzed and analyzed. Comparisons for the various parameters (yields, gas composition and carbon–hydrogen recovery) between the untreated and catalyzed reed conversion were also made.     

A simple method of electrochemical lithium intercalation within graphite from a propylene carbonate-based solution

Electrochemical lithium intercalation within graphite from 1 mol dm^− 3 solution of LiClO₄ in propylene carbonate (PC) was investigated at 25 and − 15 °C. Lithium ions were intercalated into and de-intercalated from graphite reversibly at − 15 °C despite the use of pure PC as the solvent. However, ceaseless solvent decomposition and intense exfoliation of graphene layers occurred at 25 °C. The results of the Raman spectroscopic analysis indicated that the interaction between PC molecules and lithium ions became weaker at − 15 °C by chemical exchange effects, which suggested that the thermodynamic stability of the solvated lithium ions was an important factor that determined the formation of a solid electrolyte interface (SEI) in PC-based solutions. Charge–discharge analysis revealed that the nature of the SEI formed at − 15 °C in 1 mol dm^− 3 of LiClO₄ in PC was significantly different from that formed at 25 °C in 1 mol dm^− 3 of LiClO₄ in PC containing vinylene carbonate, 3.27 mol kg^− 1 of LiClO₄ in PC, and 1 mol dm^− 3 of LiClO₄ in ethylene carbonate.     

Intercalation studies of zinc hydroxide chloride: Ammonia and amino acids

Zinc hydroxide chloride (ZHC) is a layered hydroxide salt with formula Zn₅(OH)₈Cl₂·2H₂O. It was tested as intercalation matrix for the first time and results were compared with intercalation products of the well-known zinc hydroxide nitrate and a Zn/Al layered double hydroxide. Ammonia was intercalated into ZHC, while no significant intercalation occurred in ZHN. Aspartic acid intercalation was only achieved by co-precipitation at pH=10 with ZHC and pH=8 with zinc hydroxide nitrate. Higher pH resistance in ZHC favored total deprotonation of both carboxylic groups of the Asp molecule. ZHC conferred more thermal protection against Asp combustion presenting exothermic peaks even at 452 °C while the exothermic event in ZHN was 366 °C and in the LDH at 276 °C.     

Structure characteristics contributing to flame retardancy in diazo modified novolac resins

The physical characteristics of two modified novolac resins (carbonyl phenyl azo novolac resin; CPAN and 4-(4-hydroxyphenyl azo) benzyl ester novolac resin; HPDEN) bearing nitrogen and aromatic functional groups by diazo-coupling or esterification in the branch structure of phenol novolac resin were examined. Presence of the modifiers raised the phenolic decomposition temperature (5% weight loss) from 300 °C (pure Phenolic) to 330 °C and 380 °C, while the char residue increased from 45% to 56% and 68%, respectively. The kinetics for thermal degradation energies (E_a) also rose from 151 kJ/mol K to 254 kJ/mol K (CPAN) and 273 kJ/mol K (HPDEN). The retarded decomposition kinetics is attributed both to the increase of crosslink densities and high aromatic content in the derivative resins. On the other hand, the diazo-coupling or phenyl diazenyl ester produces non-combustible gases (N₂, CO₂ and CO) during formation of aromatic char which dilute the ambient oxygen gas. Both the production of gases and the retarded kinetics due to cross-linking are definitive for the improved flame resistance.     

Physico–chemical properties of CdO–Al2O3 catalysts. I – Structural characteristics

Alumina gels AN6 and AN7 were prepared by precipitation with NaOH from hydrated aluminum sulfate at pH 6 and 7, respectively. A third alumina gel AA7 was similarly prepared, but by precipitation with 30% ammonia. Pure cadmia C8 and C9 were precipitated from cadmium sulfate at pH 8 and 9 using NaOH. Five mechanically mixed gels ACM (1:0.25), ACM (1:0.5), ACM (1:1), ACM (0.5:1) and ACM (0.25:1) were prepared by thoroughly mixing the appropriate molar ratios of AN7 and C8. Also, five coprecipitated gels ACC (1:0.25), ACC (1:0.5), ACC (1:1), ACC (0.5:1) and ACC (0.25:1) were coprecipitated by dropping simultaneously the appropriate volumes of 1 M aluminum sulfate, 1 M cadmium sulfate and 3 M NaOH. Calcination products at 400, 500, 600, 800 and 1000 °C were obtained from each preparation.TG–DTA patterns of uncalcined samples were analyzed and the XRD of all 1000 °C-products and some selected samples calcined at 400–800 °C were investigated. The thermal behaviors of pure and mixed gels depend on the precipitating agent, pH of precipitation, chemical composition and method of preparation. Generally, calcination at temperatures below 800 °C gave poorly crystalline phases. Well crystalline phases are obtained at 800 and 1000 °C. For pure alumina γ-Al₂O₃ was shown as 400 °C-calcination product that transforms into the δ form around 900 °C and later to θ-Al₂O₃ as a major phase and α-Al₂O₃ as a minor phase at 1000 °C. CdO was shown by 500 °C-calcined cadmia gel that showed color changes with rise of calcination temperature. The most stable black cadmium oxide phase (Monteponite) is obtained upon calcination at 1000 °C. Thousand degree celsius- calcined mixed oxides showed θ-Al₂O₃, α-Al₂O₃, CdAl₂O₄ and monteponite which dominate depending on the chemical composition.     

Nonstoichiometry,point defects and magnetic properties in Sr2FeMoO6−δ double perovskites

The phase stability, nonstoichiometry and point defect chemistry of polycrystalline Sr₂FeMoO_6?δ (SFMO) was studied by thermogravimety at 1000, 1100, and 1200 °C. Single-phase SFMO exists between ?10.2≤log pO₂≤?13.7 at 1200 °C. At lower oxygen partial pressure a mass loss signals reductive decomposition. At higher pO₂ a mass gain indicates oxidative decomposition into SrMoO₄ and SrFeO_3?x. The nonstoichiometry δ at 1000, 1100, and 1200 °C was determined as function of pO₂. SFMO is almost stoichiometric at the upper phase boundary (e.g. δ=0.006 at 1200 °C and log pO₂=?10.2) and becomes more defective with decreasing oxygen partial pressure (e.g. δ=0.085 at 1200 °C and log pO₂=?13.5). Oxygen vacancies are shown to represent majority defects. From the temperature dependence of the oxygen vacancy concentration the defect formation enthalpy was estimated (ΔH_OV=253±8 kJ/mol). Samples of different nonstoichiometry δ were prepared by quenching from 1200 °C at various pO₂. An increase of the unit cell volume with increasing defect concentration δ was found. The saturation magnetization is reduced with increasing nonstoichiometry δ. This demonstrates that in addition to Fe/Mo site disorder, oxygen nonstoichiometry is another source of reduced magnetization values.     

High oxygen-reduction activity of silk-derived activated carbon

Activated carbon prepared from silk fibroin, which is free of metal elements, showed a high catalytic activity for the oxygen-reduction reaction (ORR). The activated carbon had a very high onset potential of E_onset = 0.83 V (vs. RHE) in oxygen-saturated 0.5 M H₂SO₄ at 60 °C. The ORR on the activated carbon proceeded by a four-electron process in the high-electrode-potential region; this gradually decreased to a 3.5-electron reaction below about 0.6 V (vs. RHE). Only about 1% of nitrogen atoms (mostly quaternary) remained in the activated carbon by heat-treatment at up to 1200 °C are responsible for the high catalytic activity. The open circuit voltage of a polymer electrolyte fuel cell using the activated carbon as the cathode and a platinum/carbon black anode under pure oxygen and hydrogen gases, respectively, both at one atmosphere, was 0.96 V at 27 °C.     

Studies of dielectric characteristics of BaBi2Nb2O9 ferroelectrics prepared by chemical precursor decomposition method

BaBiNb₂O₉ (BBN) powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). TG–DTA showed that precursor sample got freed from organic contaminants at 575 °C. XRD showed that a single phase with the layered perovskite structure of BBN was formed after calcining at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The crystallite size (D) and the effective strain (η) were found to be 26 nm and 0.000867, respectively, while the particle size obtained from TEM was 28 ± 2 nm. SEM revealed that the average grain size after sintering at 900 °C for 4 h was ∼1.67 μm. A relative density of ∼93% was obtained using a two-step sintering process at moderate pressure. Dielectric and ferroelectric properties were investigated in the temperature range 50–500 °C and frequencies from 1 kHz to 5 MHz. Strong dispersion of the complex relative dielectric constant was observed including typical relaxor features such as shift of permittivity maximum with frequency and broadening of the peak maximum. The high dielectric constant of 545 measured at 100 kHz and other properties of BBN ceramics were compared to that of BBN prepared by other conventional methods and found to be superior.